The liquefaction, solubilization and/or extraction of fossil fuels in solid, semi-solid, viscous or highly viscous form, simply fossil fuels hereafter, have proven to be extremely challenging and thus difficult. Such fossils fuels include coal, oil shale, tar sands, crude oil and heavy crude oil, which contain organic matter as bitumen, kerogen, natural asphalt and/or asphaltene. This can be attributed to the fact that these fossil fuels comprise organic polymers of complex structures linked by oxygen and sulfur bonds, which are often imbedded in the matrices of inorganic compounds. An urgent and dire need exists to produce additional liquid feed stock for the manufacture of liquid and gaseous fuels as well as for various chemicals, pharmaceuticals and engineered materials: The demand and consumption for them are increasing very rapidly. Various technologies or processes have been invented to liquefy, solubilize and/or extract the fossil fuels. Nevertheless, none of liquefaction, solubilization and extraction technologies or processes has proven to be commercially viable on a large scale for all types of fossil fuels. This is due to the fact that every liquefaction, solubilization or extraction technology or process invented to date is exceedingly expensive to deploy and operate; moreover, such a technology or process is profoundly convoluted to scale up, operate and/or control because of one or more of the following reasons: (1) operating at an inordinately elevated pressure; (2) operating at a very high temperature; (3) needing to use expensive processing vessels and equipment requiring the external supply of hydrogen under extreme conditions; (4) being subjected to a mixture, or composition, of two or more reagents, catalysts and/or promoters, which are frequently highly toxic and are neither renewable nor recyclable; (5) requiring to supply a special form of energy, e.g., microwave radiation; (6) requiring an unusually long time even for partial liquefaction, solubilization or extraction; (7) requiring extraordinarily fine particles with a size of about 200 mesh (0.074 mm), which is profoundly difficult and costly to manufacture and handle; and (8) being incapable of recovering and recycling the necessary reagents, catalysts and/or promoters. Typical or well-known processes invented to date, all of which suffer from one or more of these major deficiencies, are outlined in the following.
German Pat. No. DE 2613122 19761014 (1976) discloses a process that causes liquefaction and desulfurization of finely divided coal suspended in a liquid tar or residual oil, in contact with H or synthesis gas and a catalyst such as Co—Mo/Al2O3 at 375-475° C. Where synthesis gas is used, Na2CO3 may be used in combination with Co—Mo.
U.S. Pat. No. 4,021,329 (1977) discloses a process for dissolving sub-bituminous coal by heating said coal in the presence of a hydrogen donor oil, gaseous carbon monoxide, water, hydrogen, and an iron compound promoted with an alkali or alkali precursor at a temperature of from about 400 degree to about 425 degree C. and at a total pressure of from about 2000 to about 5000 psig.
U.S. Pat. No. 4,060,479 (1977) discloses a process for obtaining oil, gas, sulfur and other products from shale whereby there is effected drying, pyrolysis, gasification, combustion and cooling of pyrobituminous shale or similar rocks in a single passage of said shale continuously in a moving bed, the charge and discharge of the shale being intermittent and wherein the maximum temperature of the bed is maintained in the range of about 1050° C. to 1200° C. (1900° F. to 2200° F.) or higher. The shale is essentially completely freed from the organic matter, fixed carbon and sulfur, resulting in a clean solid residue which can be disposed of without harming the ecology.
U.S. Pat. No. 4,108,760 (1978) discloses an invention related to the extraction of oil shales and tar sands by using a solvent under supercritical conditions at a temperature within 200° C. or its critical temperature in order to effect extraction of kerogen from the sand or shale. In the case of shales considerable heat needs to be applied to the shale before effective extraction can occur and extraction in this case may be carried out at a temperature within the range of 370° to 450° C.
U.S. Pat. No. 4,191,630 (1980) discloses a continuous process to produce shale oil from oil shales. It comprises an improvement, the purpose of which is to remove relatively small and up to substantial amounts of the water present as steam; and to prevent pitch formation, and “stickiness” in a second or retorting stage of the process, carried out at a much higher temperature. The first step may utilize a fixed vertical vessel in one aspect of the process or alternately a much smaller rotating horizontal vessel than that used in the second step of the process. The first step is conducted at a temperature from ambient, possibly 212° F. up to 550° F. The second or retorting step is conducted at 800° F. to 1000° F. Indirect heating of the oil shales is employed in all cases.
U.S. Pat. No. 4,338,183 (1982) discloses a process in which a solid carbonaceous material, such as coal, is converted to liquid products and the asphaltene content of a heavy hydrocarbonaceous liquid is reduced. In the process, the solid is solvent extracted by the heavy hydrocarbonaceous liquid and a hydrocarbonaceous recycle stream with a finely divided, unsupported metal catalyst and the resultant mixture of liquids is recovered as the product.
U.S. Pat. No. 4,396,491 (1983) discloses a process for extracting oil shale or tar sands under non-thermally destructive conditions with a solvent liquid containing a compound having the general formula:
where M is a carbon, sulfur, or phosphorus atom, R2 and R3 are each a hydrogen atom or a lower alkyl group, R and R1 are each a lower alkyl group, another
a monocyclic aromatic group, or R1 can be another
or R1 and R2 together can represent the atoms necessary to close a heterocyclic ring, and n=1 where M=phosphorus and is otherwise 0, to substantially remove the non-fixed carbon content of the oil shale or tar sands, leaving a solid residue of fixed carbon, ash minerals, and non-extractable matter.
U.S. Pat. No. 4,419,214 (1983) discloses a method of recovering hydrocarbon substances such as oil and tar from naturally occurring mineral matter such as oil shale and young coal ranks, which comprises subjecting the natural mineral product to microwave irradiation in a pressure vessel through which an expelling medium is passed. The expelling medium can be gaseous or liquefied carbon dioxide containing natural or mixed gases, hydrocarbon-containing gas, vapor or liquid and gaseous or vapor-halogenated hydrocarbons.
U.S. Pat. No. 4,461,696 (1984) discloses a process for converting organic material of oil-shale to predominantly liquids. The oil-shale is first heated to a temperature from about 360° C. to 475° C. in an inert atmosphere. The resulting liquids and gases are collected and the residue is extracted with a microemulsion capable of extracting organic material from the heat treated oil-shale.
U.S. Pat. No. 4,443,323 (1984) discloses a process for the oil extraction from oil sand comprising: mixing oil sand, cyclodextrin, a hydrocarbon solvent, a flocculating agent and water with one another to prepare a suspension, leaving the suspension to stand or centrifuging it to separate into an oil, a water and a sand layer, and then collecting the oil layer.
U.S. Pat. No. 4,438,816 (1984) discloses a process for the recovery of hydrocarbonaceous oil from oil shale. The process comprises: (a) heating the shale in the presence of a non-combustion supporting, non oil-miscible gas at subcritical conditions of said gas and at a temperature from about 650° F. to about 825° F. to produce a solvent extractable material and to liberate at least a first portion of the hydrocarbon contained therein; and (b) contacting the resulting solvent extractable material with a normally-liquid solvent at subcritical, reflux conditions of said solvent to liberate at least a second portion of the hydrocarbon contained in said solvent extractable material.
U.S. Pat. No. 4,485,869 (1984) discloses a method of electromagnetic heating in situ to recover liquid hydrocarbons from an oil shale formation containing kerogen in an inorganic matrix where the formation is substantially impermeable to fluids under native conditions. A block of the oil shale formation is substantially uniformly heated in situ with electromagnetic power to a temperature of about 275° C. where there is pyrolysis of a portion of the kerogen to gas and shale oil at a pressure sufficient to overcome the capillary pressure of the shale oil in the matrix, thereby providing substantial fluid permeability to the formation. The gas thereupon escaping from said block and the shale oil driven thereby are recovered, thereby further increasing the permeability of the formation. The magnitude of the electromagnetic power is controlled to raise the temperature of the block relatively slowly to increase the rate of pyrolysis of the kerogen as the permeability of the formation increases to produce gas at pressures above the necessary to overcome the capillary pressure and below that at which there is substantial escape of the gas bypassing shale oil within the formation rather than driving the oil before it.
U.S. Pat. No. 4,541,916 (1985) discloses a process for converting coal to liquid hydrocarbonaceous products involving a liquefaction reaction in the presence of a coal derived recycle slurry and a non-coal derived solvent comprising a hydrocarbonaceous oil or distillation bottom residue thereof intrinsically contaminated with greater than 300 ppm total of vanadium and nickel. The liquefaction reaction is performed under hydrogen pressure (approximately 500-4000 psi) and under elevated temperature (approximately 300.degree.-500° C.) using a weight ratio of non-coal derived solvent to coal of about 1/1 or less. The conversion of coal to liquids is greatly enhanced by the use of such a non-coal derived solvent under these conditions.
U.S. Pat. No. 4,539,093 (1985) discloses a hydrocarbon extraction process and apparatus for removing hydrocarbons from a hydrocarbon containing ore such as a diatomite ore. The ore is preprocessed to the extent required to produce an extractable ore and subsequently mixed with a carrier to form an ore stream. The carrier may be a nonaqueous solvent and may further comprise a non-porous granular material such as sand. The ore stream is passed in substantially vertical countercurrent flow through a nonaqueous solvent to produce a product-solvent stream and a spent ore stream. The solvent is subsequently separated from the hydrocarbon stream, which may be further upgraded by removal of a heavy portion. This may be accomplished in the presence of a substantial amount of fines.
U.S. Pat. No. 4,533,460 (1985) discloses a process by which hydrocarbon liquids are recovered from oil shale and other solids containing organic matter by passing a liquid organic solvent downwardly through an extraction zone in contact with said solids at an elevated pressure sufficient to maintain said solvent in the liquid phase and at a temperature below about 900° F., preferably between about 650° F. and about 900° F., in order to extract hydrocarbons from the solids into the solvent. The extracted hydrocarbons are then recovered from the solvent by fractionation. Normally, heat is supplied to the extraction zone by passing a hot, nonoxidizing gas, preferably an oxygen-free gas generated within the process, downwardly through the extraction zone in cocurrent flow with the liquid organic solvent.
U.S. Pat. No. 4,772,379 (1988) discloses a new technology for the extraction of liquid hydrocarbon products from fossil fuel resources such as oil shale, tar sands, heavy oils and coals, which comprises the mixing of a donor solvent with the fossil fuel and the exposure of the mixture to ionizing radiation. The donor solvent supplies hydrogen for combination with molecules whose bonds are broken by the irradiation process. The method may be conducted at or above ambient temperatures and pressures.
U.S. Pat. No. 4,856,587 (1989) discloses an invention comprising a method and apparatus for recovering oil from so-called depleted oil fields and also from tar sands. A pressurized, heated, non-aqueous gas, such as carbon dioxide, is continuously flowed through a channel which is in heat exchange relationship with an oil-bearing matrix, thus reducing the viscosity and mobilizing the oil in the sensible boundary region. Mobilized oil flows to a collection reservoir from which it is then produced.
U.S. Pat. No. 4,929,341 (1990) discloses a process by which an oil bearing soil is contacted in a contacting zone with a liquid medium comprising water and a lipophilic solvent which is miscible or soluble with water. The medium can include a yield improving agent comprising a water soluble acidic ionic salt or a water soluble ionic acid. The contacting produces an emulsion which comprises the oil from the oil bearing soil and the liquid medium. The inorganic portion of the soil is dispersed in the emulsion and it is separated from the emulsion by gravity or other suitable means. The emulsion is broken by an emulsion breaking agent into two phases. The two phases are allowed to separate into two layers. The first layer comprises the oil and minor amounts of the liquid medium. The second layer comprises the liquid medium and minor amounts of the oil. The first layer is then recovered. The medium from the second layer can be recycled into the contacting zone.
U.S. Pat. No. 5,998,640 (1999) discloses a method and apparatus for continuously removing oil from oil-bearing solids such as tar sands, vegetables or other solid materials using a solvent. By providing a pressure differential between the exterior and interior of an oil extraction chamber, substantially oil free solids may be removed from the oil extraction chamber through a solids extraction channel without removing any substantial volume of solvent through the solids extraction channel.
U.S. Pat. No. 6,013,158 (2000) discloses an apparatus for forming liquid hydrocarbons from solid coal. The coal is pulverized to provide a particulate coal feed, which is then extruded to provide a hollow tube of compressed coal supported inside of a support tube. A clay feed is extruded to provide a hollow tube of compressed clay supported inside of the coal tube and a combustible fuel is burned inside of the clay tube. The temperature of combustion is sufficient to fire the extruded clay and pyrolyze the extruded coal to produce hydrocarbon gases and coal char. The support tube has holes for releasing the hydrocarbon gases, which contain suspended particles formed during combustion. The suspended particles are removed from the hydrocarbon gases to provide clean gases, which are passed through an ionizing chamber to ionize at least a portion thereof. The ionized gases are then passed through a magnetic field to separate them from each other according to their molecular weight. Selected portions of at least some of the separated gases are mixed, and the mixed gases are cooled to provide at least one liquid hydrocarbon product of predetermined composition. Portions of the separated gases may also be mixed with the coal char and other input streams, such as waste plastics, and further treated to provide other hydrocarbon products.
U.S. Pat. No. 6,319,395 (2001) discloses a continuous process for producing synthetic crude oil from oil bearing material, e.g., oil shale or tar sand, through continuous process for producing synthetic crude oil from bituminous tar sand or shale. The process includes treating the tar sand or shale to produce a fluidizable feed, feeding the fluidizable feed to a fluidized bed reactor, and fluidizing and reacting the fluidizable feed in the fluidized bed reactor with substantially only hydrogen at a temperature of at least 900° F.
U.S. Pat. No. 6,936,159 (2005) discloses a process for recovering hydrocarbons from coal or oil shale. The process involves the steps of forming a pulp of finely divided coal or oil shale in a first reaction bed, adding concentrated sulphuric acid to the first reaction bed, controlling the temperature of the first reaction bed to produce a hydrocarbon mixture, and deacidifying the hydrocarbon mixture.
One of the available technical articles [“Effects of Amines Added on Banko Coal Liquefaction,” by A. Arso and M. Iino, in Fuel Processing Technology, Vol. 88, pp. 813-816 (2007)] reports the following. The addition of about 10 wt. % of an amine from aliphatic or aromatic amines to a 1-to-2 mixture of coal and tetralin substantially increases the degree of coal conversion, which can be as much as about 50 wt. % or more, when the direct liquefaction of coal with the size of about 200 mesh (74 μm or 0.074 mm) is carried out at temperatures in the range between 300 and 450° C. under the pressure of at least 90×105 (90 atm).